Note: Descriptions are shown in the official language in which they were submitted.
202000377 1
Amino-functional polybutadienes having polyether radicals in comb positions
and process for
preparation thereof
The invention relates to a process for preparing polyether-modified amino-
functional polybutadienes and to
polyether-modified amino-functional polybutadienes preparable by this process.
Polybutadienes having pendant polyether radicals are known and are prepared
according to the prior art,
for example, by a reaction of reactive functionalized polybutadienes with
polyethers. For instance, Q. Gao
et. al. in Macromolecular Chemistry and Physics (2013), 214(15), 1677-1687
describe amphiphilic polymer
comb structures that are prepared by grafting polyethylene glycol onto a main
polybutadiene chain.
According to J P 2011038003, polybutadienes functionalized with maleic
anhydride units are reacted with
amino-terminated polyethers. The result is maleinized polybutadienes having
polyether radicals in comb
positions, attached via an amide or imide group. In a similar process,
according to J. Wang, J ournal of
Applied Polymer Science (2013), 128(4), 2408-2413, polyethylene glycols are
added onto polybutadienes
having a high proportion of 1,2-butadiene monomer units to form an ester
linkage. High molecular weight
graft polymers having comb structure are obtained by the process disclosed in
J P 2002105209 by an
addition of epoxidized polybutadienes with OH-functional polyethers. H. Decher
et al., according to Polymer
International (1995), 38(3), 219-225, use the addition of isocyanate-
terminated polyethylene glycols onto
hydroxy-functional polybutadienes.
Also known are processes for preparing polyether-modified polybutadienes in
which hydroxy-functional
polybutadienes are reacted with epoxy compounds. For example, the prior art
discloses the alkoxylation of
OH-terminated polybutadienes.
US 4994621 A describes, for example, the alkoxylation of hydroxy-terminated
polybutadienes with ethylene
oxide and propylene oxide in the presence of tetramethylammonium hydroxide.
The use of hydroxy-
terminated polybutadienes in alkoxylation leads exclusively to polyether-
polybutadiene-polyether triblock
structures. According to EP 2003156 Al, this block structure is responsible
for the poor miscibility with other
reaction components in the preparation of polyurethanes.
As well as the alkoxylation of hydroxy-terminated polybutadienes, the
alkoxylation of pendantly hydroxy-
functional polybutadienes is also known. For instance, Q. Gao et. al. in
Macromolecular Chemistry and
Physics (2013), 214(15), 1677-1687 describe the preparation of a pendantly
polyether-modified
polybutadiene by alkoxylation of a pendantly hydroxy-functional polybutadiene
with ethylene oxide. The
pendantly hydroxy-functional polybutadiene used here is prepared first by
epoxidation of a polybutadiene,
followed by reaction of the epoxidized polybutadiene with a lithium-
polybutadiene compound, and finally
protonation of the reaction product with methanolic HCI. This process leads to
a polybutadiene having both
pendant polyether radicals, and also pendant polybutadiene radicals. According
to the process disclosed
in the as yet unpublished document PCT/EP2020/083013, polybutadienes modified
with polyether radicals
in comb positions are prepared by alkoxylation of pendantly hydroxy-functional
polybutadienes, which have
been obtained previously by ring-opening of epoxy-functional polybutadienes,
preferably with alcohols.
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The chemical modification of polybutadiene with the aid of epoxidation and
subsequent epoxide ring-
opening by reaction with amines is known. J P 63288295 discloses the reaction
of epoxy-functional
polybutadienes with dimethylamine and the subsequent protonation of the amine
functions with acetic acid.
The method according to J P 57205596 includes, in addition to the epoxide ring-
opening with
dimethylamine, the further quaternization of the amine functions with
epichlorohydrin. A method for epoxide
ring-opening of hydrogenated polybutadienes with amines is disclosed in DE
2554093. DE 2943879, DE
2732736 and J P 49055733 describe the addition of diethanolamine. J P 48051989
likewise describes the
addition of diethanolamine, followed by a crosslinking reaction in the
presence of dibenzoyl peroxide.
J P 53117030, DE 2734413 and DE 2943879 describe the addition of ethanolamine,
J P 05117556 the
reaction with diisopropanolamine, EP 0351135, EP 0274389 and DE 3305964 the
reaction of the epoxy
groups with dimethylamine. DD 296286 discloses the addition of primary and
secondary amines having 4
to 20 carbon atoms onto epoxidized polybutadienes in polar solvents. Further
alkoxylation of the amino-
functional polybutadienes is not disclosed in any of these documents.
The prior art to date, therefore, has not disclosed any process for preparing
preferably linear amino-
functional polybutadienes having pendant polyether chains by a simple direct
alkoxylation reaction of
pendantly amino-functional polybutadienes with alkylene oxides, wherein the
pendantly amino-functional
polybutadienes are prepared from epoxy-functional polybutadienes by a ring-
opening reaction with amines.
Polybutadienes and modified polybutadienes are in many cases used as reactive
component or formulation
constituent in order, for example, to render polymers hydrophobic or to
flexibilize them and improve
mechanical properties. At present, however, there are frequently limits to the
possible uses of polyether-
modified polybutadienes as a result of the restriction to a small number of
available triblock structures.
There has therefore been no way of varying to a large degree the chemical
makeup of the polyether-
modified polybutadienes. Moreover, there is no simple preparation process for
such polymers.
The object of the present invention was that of overcoming at least one
disadvantage of the prior art.
A particular problem addressed was that of providing an improved process for
preparing preferably linear
polybutadienes modified with polyether radicals in comb (pendant, lateral)
positions via an amino group.
The process should also enable a simple route in terms of process technology
terms to preferably linear
polybutadienes having pendant polyether radicals. The polyether-modified
polybutadienes should at the
same time also be obtainable by direct alkoxylation of pendantly amino-
functional polybutadienes. An
additional problem addressed here was that of providing suitable pendantly
amino-functional
polybutadienes as precursors and chain starters for alkoxylation in the
process.
It has now been found that, surprisingly, this problem is solved by a process
for preparing polyether-
modified amino-functional polybutadienes that comprises the following steps:
a) reacting at least one polybutadiene (A) with at least one epoxidizing
reagent (B) to give at least one
epoxy-functional polybutadiene (C);
b) reacting the at least one epoxy-functional polybutadiene (C) with at
least one amino-functional
compound (D) to give at least one hydroxy- and amino-functional polybutadiene
(E);
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C) reacting the at least one hydroxy- and amino-functional
polybutadiene (E) with at least one epoxy-
functional compound (F) to give at least one polyether-modified amino-
functional polybutadiene (G).
It has further been found that, surprisingly, polybutadienes in particular
having a high proportion of 1,4 units
and a low content of vinylic 1,2 units, after epoxidation with hydrogen
peroxide, can be converted by ring-
opening with primary or secondary amines to pendantly hydroxy- and amino-
functional polybutadienes and
can then be alkoxylated with alkylene oxides.
The object of the present invention is therefore achieved by the subject
matter of the independent claims.
Advantageous configurations of the invention are specified in the subordinate
claims, the examples and
the description.
The subject matter of the invention is described by way of example below but
without any intention that the
invention be restricted to these illustrative embodiments. Where ranges,
general formulae or classes of
compounds are specified below, these are intended to encompass not only the
corresponding ranges or
groups of compounds that are explicitly mentioned but also all subranges and
subgroups of compounds
that can be obtained by removing individual values (ranges) or compounds.
Where documents are cited in
the context of the present description, the entire content thereof is intended
to be part of the disclosure
content of the present invention.
Where average values are reported hereinafter, these values are numerical
averages unless stated
otherwise. Where measurement values, parameters or material properties
determined by measurement
are reported hereinafter, these are, unless stated otherwise, measurement
values, parameters or material
properties that are measured at 25 C and also preferably at a pressure of 101
325 Pa (standard pressure).
In the context of the present invention, number-average molar mass Mn, weight-
average molar mass Mw
and polydispersity (Mw/Mn) are preferably determined by gel-permeation
chromatography (GPC), as
described in the examples unless explicitly stated otherwise.
Where numerical ranges in the form "X to Y" are reported hereinafter, where X
and Y represent the limits
of the numerical range, this is synonymous with the statement "from at least X
up to and including Y", unless
stated otherwise. Statements of ranges thus include the range limits X and Y,
unless stated otherwise.
The terms pendant, lateral and in comb positions are used synonymously.
Wherever molecules/molecule fragments have one or more stereocentres or can be
differentiated into
isomers on account of symmetries or can be differentiated into isomers on
account of other effects, for
example restricted rotation, all possible isomers are included by the present
invention.
The formulae (1) to (5) below describe compounds or radicals that are
constructed from repeat units, for
example repeat fragments, blocks or monomer units, and can have a molar mass
distribution. The
frequency of the repeat units is reported by indices. The indices used in the
formulae should be regarded
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as statistical averages (numerical averages) unless explicitly stated
otherwise. The indices used and also
the value ranges of the reported indices should thus be regarded as averages
of the possible statistical
distribution of the structures that are actually present and/or mixtures
thereof, unless explicitly stated
otherwise. The various fragments or repeat units of the compounds described in
the formulae (1) to (5)
below may be distributed statistically. Statistical distributions are of
blockwise construction with any desired
number of blocks and with any desired sequence or are subject to a randomized
distribution; they may also
have an alternating construction or else form a gradient over the chain, where
one is present; in particular
they can also form all mixed forms in which groups having different
distributions may optionally follow one
another. The formulae below include all permutations of repeat units. Where
compounds such as
polybutadienes (A), epoxy-functional polybutadienes (C), hydroxy- and amino-
functional polybutadienes
(E), polyether-modified amino-functional polybutadienes (G) or polyether-
modified amino-functional
polybutadienes (K) containing end-capped polyether radicals, for example, that
can have multiple instances
of different units are described in the context of the present invention,
these may thus occur in these
compounds either in an unordered manner, for example in statistical
distribution, or in an ordered manner.
The figures for the number or relative frequency of units in such compounds
should be regarded as an
average (numerical average) over all the corresponding compounds. Specific
embodiments may lead to
restrictions on the statistical distributions as a result of the embodiment.
For all regions unaffected by such
restriction, the statistical distribution is unchanged.
The invention thus firstly provides a process for preparing one or more
polyether-modified amino-functional
polybutadienes, comprising the steps of:
a) reacting at least one polybutadiene (A) with at least one epoxidizing
reagent (B) to give at least one
epoxy-functional polybutadiene (C);
b) reacting the at least one epoxy-functional polybutadiene (C) with at least
one amino-functional
compound (D) to give at least one hydroxy- and amino-functional polybutadiene
(E);
c) reacting the at least one hydroxy- and amino-functional polybutadiene (E)
with at least one epoxy-
functional compound (F) to give at least one polyether-modified amino-
functional polybutadiene (G).
It is preferable that the process of the invention additionally includes at
least one of the following steps:
d) reacting the at least one polyether-modified amino-functional polybutadiene
(G) with at least one end-
capping reagent (H) to give at least one polyether-modified amino-functional
polybutadiene (K)
containing end-capped polyether radicals;
e) lightening the colour of the at least one polyether-modified amino-
functional polybutadiene (G) or (K);
f) converting at least some amino groups of the at least one polyether-
modified amino-functional
polybutadiene (G) or (K) to quatenary ammonium groups by means of an acid
and/or a quaternizing
reagent.
The steps a), b), c), d), e) and f) are carried out in the stated sequence,
where one or more of the steps d),
e) and f) may be omitted. The steps may follow each other directly. The
process may however have further
upstream steps, intermediate steps or downstream steps, such as purification
of the reactants, the
intermediates and/or the end products.
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The polybutadienes (E) prepared from the epoxy-functional polybutadienes (C)
by epoxide ring-opening
with amines are characterized in that they have both pendant amino groups and
hydroxyl groups.
Depending on the reaction conditions in step c), the addition of the epoxy-
functional compounds (F) occurs
on the amino groups, on the hydroxyl groups or preferably on both reactive
groups.
It is preferable in this case, during the process according to the invention,
to stabilize the reactants,
intermediates and products using stabilizers or antioxidants in order to avoid
unwanted polymerization
reactions of the double bonds. Suitable for this purpose are, for example, the
sterically hindered phenols
known to those skilled in the art, commercially available, for example, as
Anox 20, Irganox 1010 (BASF),
Irganox 1076 (BASF) and Irganox 1135 (BASF).
It is further preferable to conduct one or more or all process steps under an
inert atmosphere, for example
under nitrogen. The unmodified reactants, i.e. the at least one polybutadiene
(A) and also the polyether-
modified finished products according to the invention, i.e. the at least one
polyether-modified polybutadiene
(G) or (K), should also preferably be stored as far as possible with exclusion
of air.
The process according to the invention makes it possible for the first time to
modify linear polybutadienes
by a simple direct alkoxylation on the pendant amino and hydroxyl groups with
polyether radicals in comb
positions. The chain length and monomer sequence in the polyether radical may
be varied within wide
ranges. The average number of polyether radicals bonded to the polybutadiene
is adjustable in a controlled
manner via the degree of epoxidation and the functionalization with amino and
hydroxyl groups, and opens
up a great structural variety in the hydroxy- and amino-functional
polybutadienes (E).
The amino-functional polybutadienes having polyether radicals in comb
positions that are obtainable in
accordance with the invention are preferably essentially free of residual
epoxy groups. The process product
according to the invention preferably contains essentially no free polyether
components. Preferably,
essentially the polyethers are chemically attached to the polybutadiene via a
nitrogen atom and/or via an
oxygen atom.
Step a)
In step a) of the process according to the invention, at least one
polybutadiene (A) is reacted with at least
one epoxidizing reagent (B) to give at least one epoxy-functional
polybutadiene (C).
In this reaction double bonds of the polybutadiene (A) are converted to epoxy
groups. Various methods of
epoxidizing polybutadienes, for example with percarboxylic acids and hydrogen
peroxide, are known to the
person skilled in the art and are disclosed, for example, in CN 101538338, J P
2004346310, DD 253627
and WO 2016/142249 Al. Performic acid is particularly suitable for preparation
of the epoxy-functional
polybutadienes (C) having a high proportion of 1,4 units, and can be formed in
situ from formic acid in the
presence of hydrogen peroxide. The epoxidation preferably takes place in a
solvent such as toluene or
chloroform, which is removed by distillation after the reaction and after the
washing-out of any peroxide
residues.
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The polybutadienes (A) are polymers of buta-1,3-diene. The polymerization of
the buta-1,3-diene
monomers is effected essentially with 1,4 and/or 1,2 linkage. 1,4 linkage
leads to what are called 1,4-trans
units and/or 1,4-cis units, which are also referred to collectively as 1,4
units. 1,2 linkage leads to what are
called 1,2 units. The 1,2 units bear a vinyl group and are also referred to as
vinylic 1,2 units. In the context
of the present invention, the 1,2 units are also referred to as "(X)", the 1,4-
trans units as "(Y)", and the 1,4-
cis units as "(Z)":
.
...N.
--1- -
.
1,2 unit (X) 1,4-trans unit (Y) 1,4-cis unit (Z)
The double bonds present in the units are referred to analogously as 1,4-trans
double bonds, 1,4-cis double
bonds, or as 1,2 double bonds or 1,2 vinyl double bonds. The 1,4-trans double
bonds and 1,4-cis double
bonds are also referred to collectively as 1,4 double bonds.
The polybutadienes (A) are thus unmodified polybutadienes. The polybutadienes
(A) and their preparation
processes are known to the person skilled in the art. Preparation is
preferably effected by means of a free-
radical, anionic or coordinative chain polymerization.
Free-radical chain polymerization is preferably conducted as an emulsion
polymerization. This leads to
statistical occurrence of the three units mentioned. In the case of a low
reaction temperature (about 5 C),
there is a fall in the proportion of vinyl groups. Initiation is preferably
effected with potassium peroxodisulfate
and iron salts, or else with hydrogen peroxide.
In anionic chain polymerization, the chain polymerization is preferably
initiated with butyllithium. The
polybutadiene (A) thus obtained contains about 40% 1,4-cis units and 50% 1,4-
trans units.
In the case of coordinative chain polymerization, preference is given to using
Ziegler-Natta catalysts,
especially stereospecific Ziegler-Natta catalysts, that lead to a
polybutadiene (A) having a high proportion
of 1,4-cis units.
The polymerization of 1,3-butadiene, due to side reactions or further
reactions, for example a further
reaction of the double bonds of the resulting 1,2 and 1,4 units of the
polybutadiene, may also result in
branched polybutadienes (A). However, the polybutadienes (A) used in
accordance with the invention are
preferably linear, i.e. unbranched, polybutadienes. It is also possible that
the polybutadienes include small
proportions of units other than 1,2 units, 1,4-trans units or 1,4-cis units.
However, it is preferable that the
proportion by mass of the sum total of 1,2 units, 1,4-trans units and 1,4-cis
units is at least 80%, preferably
at least 90%, especially at least 99%, based on the total mass of the at least
one polybutadiene (A), i.e.
based on the total mass of all polybutadienes (A) used.
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For the process according to the invention, preference is given to using those
polybutadienes (A) that have
0% to 80% 1,2 units and 20% to 100% 1,4 units, more preferably 0% to 30% 1,2
units and 70% to 100%
1,4 units, still more preferably 0% to 10% 1,2 units and 90% to 100% 1,4
units, and most preferably 0% to
5% 1,2 units and 95% to 100% 1,4 units, based on the sum total of 1,2 units
and 1,4 units.
It is therefore preferable that, of the double bonds of all the polybutadienes
(A) used, 0% to 80% are 1,2
vinyl double bonds and 20% to 100% are 1,4 double bonds, more preferably 0% to
30% are 1,2 vinyl double
bonds and 70% to 100% are 1,4 double bonds, even more preferably 0% to 10% are
1,2 vinyl double bonds
and 90% to 100% are 1,4 double bonds, most preferably 0% to 5% are 1,2 vinyl
double bonds and 95% to
100% are 1,4 double bonds.
For the inventive preparation of the products, accordingly, preference is
given to using polybutadienes (A)
of the formula (1)
1 .
1 z
- -
i -
Formula (1)
having a content of 0% to 80% 1,2 vinyl double bonds (index x) and 20% to 100%
1,4 double bonds, more
preferably 0% to 30% 1,2 vinyl double bonds and 70% to 100% 1,4 double bonds,
even more preferably
0% to 10% 1,2 vinyl double bonds and 90% to 100% 1,4 double bonds, most
preferably having 0% to 5%
1,2 vinyl double bonds and 95% to 100% 1,4 double bonds. The ratio of 1,4-
trans double bonds (index y)
and 1,4-cis double bonds (index z) is freely variable.
The indices x, y and z give the number of the respective butadiene unit in the
polybutadiene (A). The indices
are numerical averages (number averages) over the entirety of all
polybutadiene polymers of the at least
one polybutadiene (A).
The average molar mass and polydispersity of the polybutadienes (A) of formula
(1) used is freely variable.
It is preferable that the number-average molar mass Mn of the at least one
polybutadiene (A) is from
200 g/mol to 20 000 g/mol, more preferably from 500 g/mol to 10 000 g/mol,
most preferably from
700 g/mol to 5000 g/mol.
Alternatively, it is preferable that the number-average molar mass Mn of the
at least one polybutadiene (A)
is from 2100 g/mol to 20 000 g/mol, more preferably from 2200 g/mol to 10 000
g/mol, most preferably from
2300 g/mol to 5000 g/mol.
It is further preferable that the at least one polybutadiene (A) has a
numerical average of 5 to 360, more
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preferably 10 to 180, most preferably 15 to 90, units selected from the group
consisting of 1,2 units, 1,4-cis
units and 1,4-trans units.
Alternatively, it is preferable that the at least one polybutadiene (A) has a
numerical average of 35 to 360,
more preferably 40 to 180, most preferably 45 to 90, units selected from the
group consisting of 1,2 units,
1,4-cis units and 1,4-trans units.
It is further preferable that the viscosity of the polybutadienes (A) used is
50 to 50 000 mPas, more
preferably 100 to 10 000 mPas, most preferably 500 to 5000 mPas (determined to
DIN EN ISO 3219:1994-
10).
Polybutadienes used with most preference are the commercially available
Polyvest 110 and Polyvest
130 products from Evonik Industries AG/Evonik Operations GmbH, having the
following typical indices:
Polyvest 110: ca. 1% 1,2 vinyl double bonds, ca. 24% 1,4-trans double bonds,
ca. 75% 1,4-cis double
bonds, number-average molar mass Mn ca. 2600 g/mol, viscosity (20 C) 700-860
mPas (to DIN EN ISO
3219:1994-10),
Polyvest 130: ca. 1% 1,2 vinyl double bonds, ca. 22% 1,4-trans double bonds,
ca. 77% 1,4-cis double
bonds, number-average molar mass Mn ca. 4600 g/mol, viscosity (20 C) 2700-3300
mPas (to DIN EN ISO
3219:1994-10).
Polybutadienes used with most preference are also the Lithene ultra AL and
Lithene ActiV 50 products
available from Synthomer PLC, having the following indices:
Lithene ultra AL: ca. 40% 1,2 vinyl double bonds, ca. 60% 1,4 double bonds,
Lithene ActiV 50: ca. 70% 1,2 vinyl double bonds, ca. 30% 1,4 double bonds,
The degree of epoxidation is determined quantitatively, for example, with the
aid of 13C NMR spectroscopy
or epoxy value titration (determinations of the epoxy equivalent according to
DIN EN ISO 3001:1999), and
can be adjusted in a controlled and reproducible manner via the process
conditions, especially via the
amount of hydrogen peroxide used in relation to the amount of double bonds in
the initial charge of
polybutadiene.
In step a) of the process according to the invention, >0% (i.e. from >0% to
100%) of all double bonds in the
at least one polybutadiene (A) are epoxidized.
It is preferable in step a) of the process according to the invention that
from >0% to <100%, more preferably
from >0% to 70%, even more preferably from 1% to 50%, still more preferably
from 2% to 40%, even more
preferably from 3% to 30% and most preferably from 4% to 20% of all double
bonds of the at least one
polybutadiene (A) are epoxidized.
Usable epoxidizing reagents (B) are in principle all epoxidizing agents known
to the person skilled in the
art. It is preferable that the epoxidizing reagent (B) is selected from the
group of the peroxycarboxylic acids
(percarboxylic acids, peracids), preferably from the group consisting of meta-
chloroperbenzoic acid,
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peroxyacetic acid (peracetic acid) and peroxyformic acid (performic acid),
especially peroxyformic acid
(performic acid). The peroxycarboxylic acids are preferably formed in situ
from the corresponding carboxylic
acid and hydrogen peroxide.
It is most preferable that the at least one epoxidizing reagent (B) comprises
performic acid which is
preferably formed in situ from formic acid and hydrogen peroxide.
The epoxidation of the at least one polybutadiene (A) takes place
preferentially at the 1,4 double bonds in
a statistical distribution over the polybutadiene chain. Epoxidation of the
1,2 double bonds can likewise take
place, and likewise takes place in statistical distribution over the
polybutadiene chain at these bonds.
However, epoxidation of the 1,2 double bonds is less favoured compared to
epoxidation of the 1,4 double
bonds. The reaction product thus contains epoxy-functional polybutadiene
polymers that differ from one
another in their degree of epoxidation. All the degrees of epoxidation stated
should therefore be regarded
as averages.
Step b)
In step b) of the process according to the invention, the at least one epoxy-
functional polybutadiene (C) is
reacted with at least one amino-functional compound (D) to give at least one
hydroxy- and amino-functional
polybutadiene (E).
An addition (addition reaction) of the at least one amino-functional compound
(D) onto the at least one
epoxy-functional polybutadiene (C) takes place in this reaction. Therefore,
this reaction takes place forming
one or more covalent bonds between the at least one amino-functional compound
(D) and the at least one
epoxy-functional polybutadiene (C). The reaction preferably comprises (at
least idealized) a reaction step
in which a nucleophilic attack takes place of at least one amino group of the
at least one amino-functional
compound (D) on at least one epoxy group of the at least one epoxy-functional
polybutadiene (C) with ring-
opening of this at least one epoxy group.
It is preferable that the at least one amino-functional compound (D) is
selected from compounds having at
least one primary and/or at least one secondary amino group, since primary and
secondary amino groups
are particularly easily added onto the epoxy groups of the polybutadiene. In
the context of the present
invention, ammonia is also included in these amino-functional compounds (D).
However, it is preferable
that the at least one amino-functional compound (D) is selected from organic
compounds having at least
one primary and/or at least one secondary amino group. It is more preferable
that the at least one amino-
functional compound (D) is selected from organic compounds having 1 to 22
carbon atoms and also at
least one primary and/or at least one secondary amino group. It is even more
preferable that the at least
one amino-functional compound (D) is selected from organic compounds having 1
to 12 carbon atoms and
also at least one primary and/or at least one secondary amino group. It is
also preferable that the amino-
functional compound (D) has precisely one primary or secondary amino group. As
a result, undesired
crosslinking reactions can be reduced or prevented. It is also preferable that
the amino-functional
compound (D) is not an aromatic amine, particularly not an aromatic primary
amine, since some aromatic
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primary amines are known to be human carcinogens. In the context of the
present invention, an aromatic
amine is understood to be those amines in which the nitrogen atom of at least
one amino group is bonded
to a carbon atom which is in turn part of an aromatic ring system.
It is further preferable that the at least one amino-functional compound (D)
is selected from the group
consisting of ammonia, alkylamines, cycloalkylamines, dialkylamines,
monoalkanolamines and
dialkanolamines. The aliphatic radicals bonded to the nitrogen may also bear
aromatic radicals or
heteroatoms such as nitrogen or oxygen. It is therefore also likewise
preferable that the at least one amino-
functional compound (D) is selected from the group consisting of diamines,
polyamines, polyetheramines
and hydroxy-functional aliphatic amines. The at least one amino-functional
compound (D) is more
preferably selected from the group consisting of alkylamines,
cycloalkylamines, dialkylamines,
monoalkanolamines, dialkanolamines and trialkanolamines, each having 1 to 22
carbon atoms and having
precisely one primary or secondary amino group. The at least one amino-
functional compound (D) is even
more preferably selected from the group consisting of alkylamines,
monoalkanolamines, dialkanolamines
and trialkanolamines, each having 1 to 12 carbon atoms and precisely one
primary or secondary amino
group. The at least one amino-functional compound (D) is most preferably
selected from the group
consisting of butylamine, isobutylamine, hexylamine, octylamine, 2-
ethylhexylamine, decylamine,
laurylamine, ethanolamine, isopropanolamine,
diethanolamine, diisopropanolamine, N-
methylethanolamine, N-methylisopropanolamine, 2-amino-2-methyl-1-propanol, 2-
amino-2-ethyl-1,3-
propanediol, tris(hydroxymethyl)aminomethane (TRIS, 2-amino-2-
(hydroxymethyl)propane-1,3-diol),
morpholine, piperidine, cyclohexylamine, N,N-dimethylaminopropylamine (DMAPA)
and benzylamine. It is
also possible here to use any desired mixtures of these amines. In the context
of the present invention, the
term "trialkanolamines" are understood to mean only those trialkanolamines
bearing primary and/or
secondary amino groups, such as tris(hydroxymethyl)aminomethane.
The molar ratio of the NH groups of the at least one amino-functional compound
(D) to the epoxy groups
of the at least one epoxy-functional polybutadiene (C) may be varied within a
wide range. It is however
preferable that the at least one amino-functional compound (D) and the at
least one epoxy-functional
polybutadiene (C) are used in such a molar ratio of NH groups to epoxy groups
that as far as possible a
quantitative conversion of all epoxy groups is achieved. It is therefore
preferable that, in step b), the total
number of NH groups in all the amino-functional compounds (D) to the total
number of epoxy groups in all
the epoxy-functional polybutadienes (C) is from 0.8:1 to 20:1, more preferably
from 0.9:1 to 10:1, even
more preferably from 1:1 to 5:1, most preferably from 1:1 to 3:1. The excess
of compound (D) may be
removed, for example by distillation, after the reaction and be reused if
required. In this connection it should
be noted that an ammonia molecule has exactly three, a primary amino group
exactly two and a secondary
amino group exactly one NH group.
The epoxide ring-opening with amines may optionally be carried out in a
solvent such as ethanol, propanol,
isopropanol or THE. Preferably, the solvent is omitted.
Preferably, the reaction is conducted in the presence of at least one
catalyst. The catalyst is optionally
homogeneously soluble in the reaction mixture, may be added as an aqueous
solution or is
CA 03215157 2023- 10- 11
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heterogeneously distributed therein as a solid.
It is preferable that the catalyst is selected from the group consisting of
Lewis acids and Bronsted acids;
more preferably from the group consisting of water, phenols, alcohols,
carboxylic acids, ammonium
compounds, phosphonium compounds and lithium bromide; even more preferably
from the group
consisting of carboxylic acids, phenols, ammonium compounds, phosphonium
compounds and lithium
bromide, even more preferably from the group consisting of carboxylic acids,
phenol and lithium bromide,
most preferably lithium bromide. The catalyst is optionally homogeneously
soluble in the reaction mixture,
may be added as an aqueous solution or is heterogeneously distributed therein
as a solid.
The type of catalyst and the amount used are selected so as to achieve very
rapid and quantitative addition
of the at least one amino-functional compound (D) onto the epoxy groups of the
at least one epoxy-
functional polybutadiene (C). Lithium bromide is preferably used, as a solid
or dissolved in water, in a
proportion by mass of 0.05% to 15.0%, preferably 0.2% to 10.0%, most
preferably 0.5% to 7.0%, based on
the mass of the at least one amino-functional compound (D).
The reaction of the at least one epoxy-functional polybutadiene (C) with the
at least one amino-functional
compound (D), optionally in the presence of a catalyst, is preferably carried
out at 50 C to 250 C, more
preferably at 80 C to 200 C.
The components are stirred for a few hours until the epoxy groups have been
converted as fully as possible.
The analysis for epoxy groups can be effected either by N MR spectroscopy
analysis or by known methods
of epoxy value titration (as described in the examples).
The reaction conditions in step b) are preferably chosen such that more than
90% of the epoxy groups
generated in step a) are converted under ring-opening. It is especially
preferable that no epoxy groups are
detectable any longer in the product from step b), i.e. in the at least one
hydroxy- and amino-functional
polybutadiene (E).
After the reaction, the possible excess amino-functional compounds (D) and
optionally solvent, water and
the catalyst are preferably removed by distillation and precipitated salts are
filtered off as required.
Each epoxy group in an epoxy-functional polybutadiene (C), after ring-opening
by an amino-functional
compound (D) of the formula A1-NH-A2, results in a repeat unit of the formula
(2a), (2b) or (2c):
A2
OH
õ.A1
N
OH A( A2 OH A2
Formula (2a) Formula (2b)
Formula (2c)
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In the formulae (2a), (2b) and (2c), the radicals Ai and Az are preferably
each independently organic
radicals, which may bear further amine or hydroxyl groups, or hydrogen
radicals. The radicals Ai and Az
may therefore comprise heteroatoms such as nitrogen and oxygen and may also be
bridged to each other
via an organic radical, such as in the case of morpholine or piperidine. The
amino-functional compound (D)
of the formula Ai-NH-Az may also be ammonia. In the case of ammonia, both Ai
and Az are hydrogen
radicals. If, for example, ethanolamine is used as amino-functional compound
(D), the radical Ai in the
formulae (2a), (2b), and (2c) is, for example a hydroxyethyl radical and the
radical Az is then a hydrogen
radical, i.e. Az = H. Each reacted epoxy group results in at least one pendant
OH group.
If a primary amine as compound (D) is reacted with an epoxy group of an epoxy-
functional polybutadiene
(C), a secondary amino group always forms having a reactive hydrogen atom on
the nitrogen atom. This
secondary amino group can add to a further epoxy group in a subsequent
reaction via the NH group and
thus link two epoxy-functional polybutadienes (C) to each other. The reaction
conditions in step b) are
preferably selected such that this linking reaction is largely suppressed.
In the case of the polybutadienes (A) having a predominant proportion of 1,4
units that are preferred in
accordance with the invention, those of the formula (2a) are predominant among
the repeat units of the
formulae (2a), (2b) and (2c).
It is preferable that the at least one hydroxy- and amino-functional
polybutadiene (E) has 20% to 100%,
more preferably 70% to 100%, even more preferably 90% to 100%, most preferably
95% to 100% repeat
units of the formula (2a), based on the total number of all repeat units of
the formulae (2a), (2b) and (2c).
The proportion of repeat units of the formulae (2a), (2b) and (2c) taken
together is >0% (i.e. from >0% to
100%), based on the total number of all repeat units of the at least one
hydroxy- and amino-functional
polybutadiene (E).
The degree of amination is accordingly >0% (i.e. from >0% to 100 %).
It is preferable that the proportion of repeat units of the formulae (2a),
(2b) and (2c) taken together is from
>0% to <100%, more preferably from >0% to 70 %, even more preferably from 1%
to 50 %, still more
preferably from 2% to 40%, still more preferably from 3% to 30% and most
preferably from 4% to 20%,
based on the total number of all repeat units of the at least one hydroxy- and
amino-functional polybutadiene
(E).
Accordingly, it is preferable that the degree of amination is from >0% to
<100%, more preferably from >0%
to 70%, even more preferably from 1% to 50%, still more preferably from 2% to
40%, still more preferably
from 3% to 30% and most preferably from 4% to 20%.
On completion of conversion in step b), the degree of amination of the hydroxy-
and amino-functional
polybutadiene (E) corresponds to the degree of epoxidation of the
corresponding epoxy-functional
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polybutadiene (C).
Step c)
In step c) of the process according to the invention, the at least one hydroxy-
and amino-functional
polybutadiene (E) is reacted with at least one epoxy-functional compound (F)
to give at least one polyether-
modified amino-functional polybutadiene (G).
The at least one hydroxy- and amino-functional polybutadiene (E) from step b)
serves, in step c), as starter
compound (starter) for the reaction with the at least one epoxy-functional
compound (F). Under ring-
opening and preferably in the presence of a suitable catalyst, the at least
one epoxy-functional compound
(F) (also referred to hereinafter simply as "monomer" or "epoxy monomer" or
"epoxide") is added onto the
NH and/or OH groups of the at least one hydroxy- and amino-functional
polybutadiene (E) in a polyaddition
reaction. This leads to the formation of amino-functional polybutadienes with
polyether chains in comb
(pendant) positions, i.e. to the formation of the at least one polyether-
modified amino-functional
polybutadiene (G). The monomers are preferably added onto (at least largely)
all OH groups and onto (at
least largely) all NH groups. The polyether-modified amino-functional
polybutadiene (G) is preferably a
linear polybutadiene which has been modified with polyether radicals in comb
(pendant) positions. It is thus
preferable that the polyether-modified amino-functional polybutadiene (G) has
a linear polybutadiene
backbone and pendant polyether radicals.
The reaction in step c) is preferably an alkoxylation reaction, i.e. a
polyaddition of alkylene oxides onto the
at least one hydroxy- and amino-functional polybutadiene (E). However, the
reaction in step c) may also be
conducted with glycidyl compounds alternatively or additionally to the
alkylene oxides.
It is therefore preferable that the at least one epoxy-functional compound
used in step c) is selected from
the group of the alkylene oxides, more preferably from the group of the
alkylene oxides having 2 to 18
carbon atoms, even more preferably from the group of the alkylene oxides
having 2 to 8 carbon atoms,
most preferably from the group consisting of ethylene oxide, propylene oxide,
1-butylene oxide, cis-2-
butylene oxide, trans-2-butylene oxide, isobutylene oxide and styrene oxide;
and/or in that the at least one
epoxy-functional compound used in step c) is selected from the group of the
glycidyl compounds, more
preferably from the group of the monofunctional glycidyl compounds, most
preferably from the group
consisting of phenyl glycidyl ether, o-cresyl glycidyl ether, tert-butylphenyl
glycidyl ether, allyl glycidyl ether,
butyl glycidyl ether, 2-ethylhexyl glycidyl ether, Cu/C14 fatty alcohol
glycidyl ether and Cu/Cm fatty alcohol
glycidyl ether.
The monomers may be added either individually in pure form, in alternating
succession in any metering
sequence, or else simultaneously in mixed form. The sequence of monomer units
in the resulting polyether
chain is thus subject to a blockwise distribution or a statistical
distribution or a gradient distribution in the
end product.
By the process according to the invention, pendant polyether chains are
constructed on the polybutadiene,
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which are exemplified in that they can be prepared in a controlled and
reproducible manner in terms of
structure and molar mass.
The sequence of monomer units can be varied by the sequence of addition within
broad limits.
The molar masses of the pendant polyether radicals may be varied within broad
limits by the process
according to the invention, and controlled specifically and reproducibly via
the molar ratio of the added
monomers in relation to the NH and OH groups of the at least one initially
charged hydroxy- and amino-
functional polybutadiene (E) from step b).
The polyether-modified amino-functional polybutadienes (G) prepared in
accordance with the invention are
preferably characterized in that they contain B radicals bonded to the
polybutadiene skeleton via an amino
and/or ether group according to the formulae (3a), (3b) and (3c)
k2
11-1¨ ¨ B
A2
>)-N
A1)11[B 1k1 12-1¨.
B -
0, 0
A2) BI
12 k2 N.)
Formula (3a) Formula (3b)
Formula (3c)
The radicals Ai and Az are each independently organic radicals preferably
having 1 to 22, most preferably
having 1 to 12 carbon atoms, where the radicals Ai and Az may be covalently
bonded to each other. The
radicals Ai and Az may comprise heteroatoms, preferably nitrogen and oxygen.
The indices kl and k2 in the formulae (3a), (3b) and (3c) are each
independently integers from 0 to 8,
preferably from 0 to 6, most preferably from 0 to 4. In addition, the indices
11 and 12 in the formulae (3a),
(3b) and (3c) are integers and each independently either 0 or 1. The radicals
B formed by alkoxylation may
therefore be bound kl-fold and k2-fold to the radicals Ai and Az respectively,
where the chemical bond is
formed via a nitrogen atom or an oxygen atom, which is part of Ai and Az. The
radicals B formed by
alkoxylation, however, may also be bonded directly to the nitrogen atom shown.
If, in the formulae (2a),
(2b) or (2c), the radical Ai or Az is a hydrogen radical, then in the formulae
(3a), (3b) or (3c) index 11 and 12
equal 0 and kl and k2 equal 1, i.e. the corresponding radical Ai or Az in the
formulae (3a), (3b) and (3c) is
non-existent and thus a polyether radical B is bonded directly to the nitrogen
atom shown. An N-H group in
the formulae (2a), (2b) or (2c) is therefore replaced by an N-B group. If, in
the formulae (2a), (2b) or (2c),
the radical Ai or Az is an organic radical, then in the formulae (3a), (3b) or
(3c) index 11 or 12 equal 1. If, in
the formulae (2a), (2b) or (2c), both Ai and Az are hydrogen radicals, then in
the formulae (3a), (3b) or
(3c) the indices 11 and 12 equal 0 and kl and k2 equal 1, i.e. the radicals Ai
and Az in the formulae (3a),
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(3b) and (3c) are non-existent and the polyether radicals B are bonded
directly to the nitrogen atom shown.
Both N-H groups in the formulae (2a), (2b) or (2c) are therefore each replaced
by an N-B group.
If a primary alkylamine, for example, is used as amino-functional compound (D)
in step b), and the alkyl
radical has no other groups reactive to epoxides, for example OH or NH groups,
then 11 = 1, kl = 0,12 = 0
and k2 = 1 for example.
If the primary amine ethanolamine, for example, is used as amino-functional
compound (D) in step b), then
Ai is a divalent radical of the formula -CH2CH20- for example, which, in this
illustration, is bonded on the
left to the nitrogen atom of the amino group via the carbon atom and is bonded
on the right to a radical B
via the oxygen atom, i.e. Ii = 1, kl = 1,12 = 0 and k2 = 1 for example.
If the primary amine tris(hydroxymethyl)aminomethane (TRIS, 2-amino-2-
(hydroxymethyl)propane-1,3-
diol), for example, is used as amino-functional compound (D) in step b), then
Ai is a tetravalent radical of
the formula -C(CH20-)3 for example, which, in this illustration, is bonded on
the left to the nitrogen atom of
the amino group via the carbon atom and is bonded in each case on the right to
a radical B via the three
oxygen atoms (and thus to three B radicals in total), i.e. Ii = 1, kl = 3,12 =
0 and k2 = 1 for example.
If the secondary amine diethanolamine, for example, is used as amino-
functional compound (D) in step b),
then Ai and Az are divalent radicals of the formula -CH2CH20- for example,
which, in this illustration, are
bonded on the left to the nitrogen atom of the amino group via the carbon atom
and are bonded on the right
to a radical B via the oxygen atom, i.e. Ii = 1, kl = 1,12 = 1 and k2 = 1.
If the secondary amine N-methylethanolamine, for example, is used as amino-
functional compound (D) in
step b), then Ai is a methyl group and Az is a divalent radical of the formula
-CH2CH20- for example, which,
in this illustration, is bonded on the left to the nitrogen atom of the amino
group via the carbon atom and is
bonded on the right to the radical B via the oxygen atom, i.e. 11 = 1, kl =
0,12 = 1 and k2 = 1.
If the secondary amine piperidine, for example, is used as amino-functional
compound (D) in step b), then
Ai and Az are covalently bonded to each other and together form the divalent
radical -CH2CH2CH2CH2CH2-
, which, in this illustration, is bonded both on the left and right to the
nitrogen atom of the amino group, i.e.:
11 = 1, kl = 0,12 = land k2 = 0.
Therefore, in the alkoxylation reaction, there results preferably in each case
precisely one pendant B radical
from (at least almost) every pendant OH and NH group of the at least one
hydroxy- and amino-functional
polybutadiene (E). The radical B is in turn constructed from one or more
monomers, preferably from two or
more monomers, of the at least one epoxy-functional compound (F) used. It is
possible, although less
preferable, that in the alkoxylation reaction not every OH or NH group of the
hydroxy- and amino-functional
polybutadiene (E) results in a pendant B radical, rather that only some, but
preferably the overwhelming
majority of the OH and NH groups are reacted in step c).
In the context of the invention, it is possible in principle to use all
alkoxylation catalysts known to the person
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skilled in the art, for example basic catalysts such as alkali metal
hydroxides, alkali metal alkoxides, amines,
guanidines, amidines, phosphorus compounds such as triphenylphosphine, and
additionally Bronsted-
acidic and Lewis-acidic catalysts such as SnCI4, SnCl2, SnF2, BF3 and BF3
complexes, and also double
metal cyanide (DMC) catalysts. Optionally, the addition of a catalyst can be
omitted.
Prior to the feeding of epoxide, i.e. prior to the addition of the at least
one epoxy-functional compound (F)
used, the reactor partly filled with the starter and optionally the catalyst
is inertized, for example with
nitrogen. This is accomplished, for example, by repeated alternating
evacuation and supply of nitrogen. It
is advantageous to evacuate the reactor to below 200 mbar after the last
injection of nitrogen. The addition
of the first amount of epoxy monomer thus preferably takes place into the
evacuated reactor. The
monomers are dosed while stirring and optionally cooling in order to remove
the heat of reaction released
and to maintain preselected reaction temperature. The starter used is the at
least one hydroxy- and amino-
functional polybutadiene (E), or else it is possible to use a polyether-
modified amino-functional
polybutadiene (G) already prepared by the process of the invention as starter,
as described further below.
In a particular embodiment, when starting the monomer addition, the addition
of a catalyst can be omitted.
This is the case, for example when the amino groups bonded to the
polybutadiene and sufficiently reactive.
If a sufficient number and nucleophilic NH functions are present on the
polybutadiene, the starter itself
catalyzes the alkoxyation reaction. The reaction rate generally declines with
the polyether chain length. To
achieve higher molecular weight polyether radicals B, it may be necessary or
beneficial to add one of the
aforementioned catalysts to the alkoxylation reaction at a later time point.
DMC catalysis
Preference is given to using zinc/cobalt DMC catalysts, in particular those
containing zinc
hexacyanocobaltate(III). Preference is given to using the DMC catalysts
described in US 5 158 922, US
20030119663, WO 01/80994. The catalysts may be amorphous or crystalline.
It is preferable that the catalyst concentration is from > 0 ppmw to 1000
ppmw, more preferably from
> 0 ppmw to 700 ppmw, most preferably from > 10 ppmw to 500 ppmw, based on the
total mass of the
products formed.
The catalyst is preferably metered into the reactor only once. The catalyst
should preferably be clean, dry
and free of basic impurities that could inhibit the DMC catalyst. The amount
of catalyst should preferably
be set so as to give sufficient catalytic activity for the process. The
catalyst may be metered in in solid form
or in the form of a catalyst suspension. If a suspension is used, then a
particularly suitable suspension
medium is the starter.
In order to start the DMC-catalysed reaction, it may be advantageous first to
activate the catalyst with a
portion of the at least one epoxy-functional compound (F), preferably selected
from the group of the alkylene
oxides, especially with propylene oxide and/or ethylene oxide. Once the
alkoxylation reaction is underway,
the continuous addition of the monomer may be commenced.
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The reaction temperature in the case of a DMC-catalysed reaction in step c) is
preferably 60 C to 200 C,
more preferably 90 C to 160 C and most preferably 100 C to 140 C.
The internal reactor pressure in the case of a DMC-catalysed reaction in step
c) is preferably from 0.02 bar
to 100 bar, more preferably from 0.05 bar to 20 bar, most preferably from 0.1
bar to 10 bar (absolute).
Most preferably, a DMC-catalysed reaction in step c) is conducted at a
temperature of 100 C to 140 C and
a pressure of 0.1 bar to 10 bar.
The reaction may be performed in a suitable solvent, for example for the
purpose of lowering the viscosity.
After the epoxide addition has ended, there preferably follows a period of
further reaction to allow the
reaction to proceed to completion. The further reaction may for example be
carried out by continued
reaction under reaction conditions (i.e. maintenance of, for example, the
temperature) without addition of
reactants. The DMC catalyst typically remains in the reaction mixture.
Once the reaction has proceeded to completion, unreacted epoxides and any
further volatile constituents
can be removed by vacuum distillation, steam or gas stripping, or other
methods of deodorization. The
finished product is finally filtered at < 100 C in order to remove any cloudy
substances.
Base catalysis
As an alternative to the DMC catalysts, it is also possible to use basic
catalysts in step c). Especially suitable
are alkali metal alkoxides such as sodium methoxide and potassium methoxide,
which are added in solid
form or in the form of their methanolic solutions. In addition, it is possible
to use all alkali metal hydroxides,
especially sodium hydroxide and/or potassium hydroxide, either in solid form
or in the form of aqueous or
alcoholic solutions, for example. In addition, it is also possible in
accordance with the invention to use basic
nitrogen compounds, preferably amines, guanidines and amidines, most
preferably tertiary amines such as
trimethyla mine and triethyla mine.
It is preferable to use the basic catalysts at a concentration of >0 mol% to
100 mol%, more preferably
>0 mol% to 50 mol%, most preferably 3 mol% to 40 mol%, based on the sum total
of OH and NH groups
in the starter.
The reaction temperature in the case of a base-catalysed reaction in step c)
is preferably 80 C to 200 C,
more preferably 90 C to 160 C and most preferably 100 C to 160 C.
The internal reactor pressure in the case of a base-catalysed reaction in step
c) is preferably from 0.2 bar
to 100 bar, more preferably from 0.5 bar to 20 bar, most preferably from 1 bar
to 10 bar (absolute).
Most preferably, the base-catalysed reaction in step c) is conducted at a
temperature of 100 C to 160 C
and a pressure of 1 bar to 10 bar.
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The reaction may optionally be performed in a suitable solvent. After the
epoxide addition has ended, there
preferably follows a period of further reaction to allow the reaction to
proceed to completion. The further
reaction can be conducted, for example, by continued reaction under reaction
conditions without addition
of reactants. Once the reaction has proceeded to completion, unreacted
epoxides and any further volatile
constituents can be removed by vacuum distillation, steam or gas stripping, or
other methods of
deodorization. Volatile catalysts, such as volatile amines, are removed here.
For neutralization of the basic crude products, acids such as phosphoric acid
or sulfuric acid or carboxylic
acids such as acetic acid and lactic acid are added. Preference is given to
the use of aqueous phosphoric
acid and lactic acid. The amount of the respective acid used is guided by the
amount of basic catalyst used
beforehand. The basic polybutadiene with pendant polyether radicals is stirred
in the presence of the acid
at preferably 40 C to 95 C and then distilled to dryness in a vacuum
distillation at < 100 mbar and 80 C to
130 C. The neutralized product is finally filtered, preferably at < 100 C, in
order to remove precipitated
salts.
It is preferable that the end products according to the invention have a water
content of <0.2% (specified
as proportion by mass based on the total mass of the end product) and an acid
number of <0.5 mg KOH/g
and are virtually phosphate-free.
Products as starters
It is not always possible to achieve the desired molar mass of the end product
in just a single reaction step,
especially the alkoxylation step. Particularly when long polyether side chains
are the aim and/or the starter
from step b), i.e.the at least one hydroxy- and amino-functional polybutadiene
(E), has a high OH and NH
group functionality, it is necessary to add large amounts of epoxy monomers.
This is sometimes not
permitted by the reactor geometry. The polyether-modified amino-functional
polybutadienes (G) prepared
in accordance with the invention from step c) bear an OH group at the ends of
each of their pendant
polyether radicals, and are therefore suitable in turn as starter for
construction of conversion products of
high molecular weight. In the context of the invention, they are precursors
and starter compounds for the
synthesis of polybutadienes having relatively long polyether radicals. The at
least one epoxy-functional
compound (F) can thus be converted in step c) in multiple component steps.
A product prepared with the aid of DMC catalysis in step c) may, in accordance
with the invention, have its
level of alkoxylation increased by new addition of epoxy monomers, either by
means of DMC catalysis or
with use of one of the aforementioned basic or acidic catalysts. It is
optionally possible to add a further
DMC catalyst in order, for example, to increase the reaction rate in the chain
extension.
A product prepared under base catalysis from step c) may be alkoxylated to
higher molar masses either
under basic or acidic conditions or by means of DMC catalysis. In step c),
neutralization is advantageously
dispensed with if the aim is to react the basic precursor further with
monomers under base catalysis. It is
optionally possible to add a further basic catalyst in order, for example, to
increase the reaction rate in the
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chain extension.
Optional step d)
In an optional further step d), the at least one polyether-modified amino-
functional polybutadiene (G) is
reacted with at least one end-capping reagent (H) to give at least one
polyether-modified amino-functional
polybutadiene (K) containing end-capped polyether radicals. This further
converts the B radicals of the
polyether-modified polybutadiene (G) having terminal hydroxyl groups to give
terminal ester, ether,
urethane and/or carbonate groups. The end-capping of polyethers is known to
those skilled in the art, for
example esterification with carboxylic acids or carboxylic anhydrides, in
particular acetylation using acetic
anhydride, etherification with halogenated hydrocarbons, in particular
methylation with methyl chloride
according to the principle of the Williamson ether synthesis, urethanization
through reaction of the OH
groups with isocyanates, in particular with monoisocyanates such as stearyl
isocyanate, and carbonation
through reaction with dimethyl carbonate and diethyl carbonate.
Optional step e)
In an optional step e), the at least one polyether-modified amino-functional
polybutadiene (G) or (K) is
lightened in colour. If the optional step e) follows optional step d), the at
least one polyether-modified amino-
functional polybutadiene (K) containing end-capped polyether radicals is
lightened in colour. If, in contrast,
the optional step d) is omitted, the optional step e) follows step c) of the
process according to the invention
and the at least one polyether-modified amino-functional polybutadiene (G) is
lightened in colour. The
lightening can be effected, for example, by adding activated carbon,
preferably in a suitable solvent, or by
treatment with hydrogen peroxide.
Optional step f)
In an optional step f), at least some of the amino groups of the at least one
polyether-modified amino-
functional polybutadiene (G) or (K) is reacted with an acid or a quaternizing
reagent such as alkyl halides
and benzyl halides, dimethyl sulfate or chloroacetic acid or sodium
chloroacetate to give quaternary
ammonium groups. Step f) may optionally be carried out after step c) or after
optional step d) or after
optional step e). After quaternization, the products may be dissolved or
dispersed, for example in water or
organic solvents.
Reactors
Reactors used for the process according to the invention may in principle be
any suitable reactor types that
allow control over the reaction and any exothermicity therein. The reaction
regime may be continuous,
semicontinuous or else batchwise in a known technical manner and can be
flexibly tailored to the production
equipment available. As well as conventional stirred-tank reactors, it is also
possible to use jet-loop reactors
with a gas phase and external heat exchanger tubes as described in WO
01/062826. In addition, it is
possible to use gas phase-free loop reactors.
CA 03215157 2023- 10- 11
202000377 20
Polyether-modified amino-function polybutadienes
The present invention further provides amino-functional polybutadienes
modified with polyether radicals in
comb (pendant, lateral) positions, as preparable by the process according to
the invention.
The invention therefore further provides a polyether-modified amino-functional
polybutadiene (G) or (K)
obtainable by the process according to the invention.
The polyether-modified amino-functional polybutadiene (G) or (K) is preferably
a linear polybutadiene which
has been modified with polyether radicals in comb (pendant, lateral)
positions. It is thus preferable that the
polyether-modified amino-functional polybutadiene (G) or (K) has a linear
polybutadiene backbone and
pendant polyether radicals.
The invention likewise further provides a polyether-modified amino-functional
polybutadiene (G) or (K)
preferably obtainable by the process according to the invention, characterized
in that the polyether-modified
amino-functional polybutadiene (G) or (K) comprises repeat units selected from
the group consisting of the
divalent radicals
ki. k2
14- 12
A2
N
Al )11 B k1 121-
_t- 1.1
0
0 A2)12 B I B
, N.)
k2
(U) (V) (W)
(X) (Y) (Z)
where
Ai and Az are each independently organic radicals preferably having 1 to 22
carbon atoms, most
preferably having 1 to 12 carbon atoms, where the radicals Ai and Az may be
covalently
bonded to each other,
is each independently a radical of the formula (4a),
CA 03215157 2023- 10- 11
202000377 21
CH3 CH3
[ Hc2 0H2 0 1 [ 0H2
F61 0 _______________________________________________ F61 0 __ CH2 0 __
CH2 F61 0 __ R4
B - ________________________
I I H I
I
m R1 n CH3 0 CH3 p R2
ci
Formula (4a);
preferably is each independently a radical of the formula (4b),
[ H2 H2 1 [ H2 H
B= ___________________________________________ C C 0 ____ C C 0 ___ R4
I
m CH3 n
Formula (4b);
most preferably is each independently a radical of the formula (4c),
[ H2 H2
H2
B= ___________________________________________ c c 01 [ C 18 01 H
I
111 CH3 n
Formula (4c);
RI- is each independently a monovalent hydrocarbon radical
having 1 to 16 carbon atoms,
preferably each independently an alkyl radical having 1 to 16 carbon atoms or
a phenyl
radical;
most preferably each independently a methyl radical, an ethyl radical or a
phenyl radical;
R2 is a radical of the formula -CH2-0-R3;
R3 is each independently a monovalent hydrocarbon radical
having 3 to 18 carbon atoms,
preferably each independently an allyl radical, a butyl radical, an alkyl
radical having 8 to
15 carbon atoms or a phenyl radical that may be substituted by monovalent
radicals
selected from hydrocarbon radicals having 1 to 4 carbon atoms;
most preferably a tert-butylphenyl radical or an o-cresyl radical;
R4 is each independently a monovalent organic radical
having 1 to 18 carbon atoms or
hydrogen, preferably hydrogen;
and
kl and k2 are each independently integers from 0 to 8, preferably from 0 to 6,
most preferably from 0
to 4;
11 and 12 are integers and each independently either 0 or 1;
m, n, o, p and q are each independently rational numbers from 0 to 300,
preferably from 0 to 200, most
preferably from 0 to 100, with the proviso that the sum total of m, n, o, p
and q is greater than 1,
preferably greater than 5, most preferably greater than 10;
the sum total of all repeating units (U), (V) and (W) divided by the sum total
of all repeating units (U),
(V), (W), (X), (Y) and (Z) is >0%;
including every permutation of the repeat units (U), (V), (W), (X), (Y) and
(Z) and of the repeat units in
the B radical.
The R1, R2, R3 and R4 radicals may each independently be linear or branched,
saturated or unsaturated,
aliphatic or aromatic, and substituted or unsubstituted.
CA 03215157 2023- 10- 11
202000377 22
H2 H
____________________________ C -C --O
1
The general notation - R -
with R = R1 or R2 in formula (4a) or R = CH3 in the formulae (4b)
H2 H
H H2
______________________________________________ C -c --o C
C 0 ___
1
1
and (4c) represents either a unit of the formula - R -
or a unit of the formula - R
H2 H
C -C --O ________________________________________
1
, but preferably a unit of the formula - R - .
CH3 -
H2 1
_____________________________ C -C --O
1
The general notation - CH3 _
in formula (4a) represents either a unit of the formula
CH3 _ CH3
H2 1 1 H2
___________ C -c --o C C 0 ___
1 1
CH3 _ or a unit of the formula _ CH3
- , but preferably a unit of the formula
CH3
H2 1
C -C --O ______________
1
CH3 - =
It is further preferable that the radical R4 is each independently selected
from the group consisting of
monovalent hydrocarbon radicals having 1 to 18 carbon atoms, acyl radicals -
C(=0)R6, urethane radicals -
C(=0)NH-R6, carbonate radicals -C(=0)0-R2 and hydrogen; R4 is more preferably
each independently
selected from the group consisting of alkyl radicals having 1 to 18 carbon
atoms, alkylene radicals having
1 to 18 carbon atoms, acyl radicals -C(=0)R5, urethane radicals -C(=0)NH-R6,
carbonate radicals -C(=0)0-
R2 and hydrogen; most preferably, R4 is hydrogen, where the term "hydrogen"
denotes a hydrogen radical.
R5 is each independently an alkyl or alkenyl radical having 1 to 18 carbon
atoms, preferably having 1 to 10
carbon atoms, most preferably a methyl radical.
R6 is each independently an alkyl or aryl radical having 1 to 18 carbon atoms,
preferably having 6 to 18
carbon atoms.
R2 is each independently an alkyl radical having 1 to 18 carbon atoms,
preferably having 1 or 2 carbon
atoms.
In accordance with the invention, the sum total (the total number) of all
repeat units (U), (V) and (W) divided
by the sum total (the total number) of all repeat units (U), (V), (W), (X),
(Y) and (Z) of the at least one
polyether-modified amino-functional polybutadiene (G) or (K) is >0%, i.e. from
>0% to 100%.
This means, inversely, that the sum total (the total number) of all repeat
units (X), (Y) and (Z) divided by
the sum total (the total number) of all repeat units (U), (V), (W), (X), (Y)
and (Z) of the at least one polyether-
CA 03215157 2023- 10- 11
202000377 23
modified amino-functional polybutadiene (G) or (K) is <100% (i.e. <100% to
0%).
This means that >0 % (i.e. from >0% to 100%) of the totality of repeat units
(U), (V), (W), (X), (Y) and (Z)
are polyether-modified.
This also means that <100% (i.e. from <100% to 0%) of the totality of repeat
units (U), (V), (W), (X), (Y)
and (Z) are not polyether-modified.
This also means that the polyether-modified amino-functional polybutadiene (G)
or (K) comprises at least
one repeat unit selected from the group consisting of (U), (V) and (W).
It is preferable here that the sum total (the total number) of all repeat
units (U), (V) and (W) divided by the
sum total (the total number) of all repeat units (U), (V), (W), (X), (Y) and
(Z) in the at least one polyether-
modified amino-functional polybutadiene (G) or (K) is preferably from >0% to
<100%, more preferably from
>0% to 70%, even more preferably from 1% to 50%, even more preferably from 2%
to 40%, still more
preferably from 3% to 30%, most preferably from 4% to 20%.
This means that preferably from >0% to <100%, more preferably from >0% to 70%,
even more preferably
from 1% to 50%, even more preferably from 2% to 40%, still more preferably
from 3% to 30%, most
preferably from 4% to 20% of the totality of repeat units (U), (V), (W), (X),
(Y) and (Z) are polyether-modified.
It is further preferable here that the sum total (the total number) of all
repeat units (X), (Y) and (Z) divided
by the sum total (the total number) of all repeat units (U), (V), (W), (X),
(Y) and (Z) in the at least one
polyether-modified amino-functional polybutadiene (G) or (K) is from <100% to
>0%, more preferably from
<100% to 30%, even more preferably from 99% to 50%, even more preferably from
98% to 60%, still more
preferably from 97% to 70%, most preferably from 96% to 80%.
This means that preferably from <100% to >0%, more preferably from <100% to
30%, even more preferably
from 99% to 50%, even more preferably from 98% to 60%, still more preferably
from 97% to 70%, most
preferably from 96% to 80% of the totality of repeat units (U), (V), (W), (X),
(Y) and (Z) are not polyether-
modified.
It is preferable that the proportion by mass of all repeat units (U), (V),
(W), (X), (Y) and (Z) taken together,
based on the total mass of the polyether-modified amino-functional
polybutadiene (G) or (K), is at least
80%, more preferably at least 90%, even more preferably at least 99%, most
preferably 100%.
It is preferable that the polyether-modified amino-functional polybutadiene
(G) or (K) consists largely or
completely of the repeat units (U), (V), (W), (X), (Y) and (Z).
It is preferable that the polyether-modified amino-functional polybutadiene
(G) or (K) is a polybutadiene of
the formula (5) that has been modified with pendant polyether radicals,
CA 03215157 2023- 10- 11
202000377 24
k1_ =k2
B B
11 4- -4-
i!kie ),A212
N
_
C',1 B
- i
r\i'(Altl[B Ik1
a b 0 - B
.\--
\
12 13 --T-I1
- B
Iv
Formula (5),
where the proportion of the polyether-modified repeat units shown in formula
(5), based on the sum total of
all repeat units shown in formula (5), is >0% (i.e. from >0% to 100%), more
preferably from >0% to <100%,
more preferably from >0% to 70%, still more preferably from 1% to 50%, even
more preferably from 2% to
40%, even more preferably from 3% to 30%, most preferably from 4% to 20%,
where the proportion is
calculated as [(d+e+f)/(a+b+c+d+e+f)]*100%.
This means that the proportion of the non-polyether-modified repeat units
shown in formula (5), based on
the sum total of all repeat units shown in formula (5), is <100% (i.e. from
<100% to 0%), preferably from
<100% to >0%, more preferably from <100% to 30%, still more preferably from
99% to 50%, even more
preferably from 98% to 60%, even more preferably from 97% to 70%, most
preferably from 96% to 80%,
where the proportion is calculated as [(a+b+c)/(a+b+c+d+e+f)]*100%.
The repeat units with the indices a, b, c, d, e and fare distributed in an
arbitrary, statistical manner over the
polybutadiene chain. All the indices reported should therefore be regarded as
averages.
It is preferable that the proportion by mass of all repeat units with the
indices a, b, c, d, e and f taken
together, based on the total mass of the polyether-modified amino-functional
polybutadiene (G) or (K), is at
least 80%, more preferably at least 90%, even more preferably at least 99%,
most preferably 100%.
It is preferable that the polyether-modified amino-functional polybutadiene
(G) or (K) consists largely or
completely of the repeat units with the indices a, b, c, d, e and f.
It is further preferable that the polyether-modified amino-functional
polybutadienes (G) or (K) are
characterized in that 0% to 80%, more preferably 0% to 30%, even more
preferably 0% to 10% and most
preferably 0% to 5%, of the double bonds present are 1,2 vinyl double bonds,
and 20% to 100%, more
preferably 70% to 100%, even more preferably 90% to 100% and most preferably
95% to 100%, of the
CA 03215157 2023- 10- 11
202000377 25
double bonds present are 1,4 double bonds.
Preference is therefore given in the context of the invention to compounds of
the formula (5) having a
content of 0% to 80% 1,2 vinyl double bonds (index a) and 20% to 100% 1,4
double bonds (sum of indices
b and c), more preferably having 0% to 30% 1,2 vinyl double bonds and 70% to
100% 1,4 double bonds,
even more preferably having 0% to 10% 1,2 vinyl double bonds and 90% to 100%
1,4 double bonds and
most preferably having 0% to 5% 1,2 vinyl double bonds and 95% to 100% 1,4
double bonds, based on
the total number of double bond-containing repeat units (sum of a + b + c).
The ratio of 1,4-trans double
bonds (index b) and 1,4-cis double bonds (index c) is freely variable.
Most preferred are compounds of the formula (5) having a content of >95% of
repeat units with index d,
based on the sum total of repeat units d + e + f. The ratio of repeat units e
and f to each other is freely
variable.
The number-average molar mass Mn, weight-average molar mass Mw and
polydispersity of the
polybutadiene component of the polyether-modified amino-functional
polybutadiene (G) or (K) are freely
variable. The polybutadiene component is understood to mean the component of
the polyether-modified
amino-functional polybutadiene (G) or (K) that originates from the
polybutadiene (A) used in the process.
In formula (5), the polybutadiene component of the polyether-modified amino-
functional polybutadiene (G)
or (K) is understood to mean the component of the polymer that results from
the polyether-modified amino-
functional polybutadiene (G) or (K) minus the radicals [B]ki(A1)11.-N-(A2)12-
[B]k2 and B-0. This also applies
accordingly to the aforementioned polyether-modified amino-functional
polybutadiene (G) or (K) comprising
repeat units selected from the group consisting of the divalent repeat units
(U), (V), (W), (X), (Y) and (Z).
It is preferable that the number-average molar mass Mn of the polybutadiene
component of the polyether-
modified polybutadiene (G) or (K) is from 200 g/mol to 20 000 g/mol, more
preferably from 500 g/mol to
10 000 g/mol, most preferably from 700 g/mol to 5000 g/mol.
Alternatively, it is preferable that the number-average molar mass Mn of the
polybutadiene component of
the polyether-modified polybutadiene (G) or (K) is from 2100 g/mol to 20 000
g/mol, more preferably from
2200 g/mol to 10 000 g/mol, most preferably from 2300 g/mol to 5000 g/mol.
The number-average molar mass Mn of the polybutadiene component is defined
here as the number-
average molar mass Mn of the underlying polybutadiene (A).
It is further preferable that the polyether-modified amino-functional
polybutadiene (G) or (K) has on average
5 to 360, preferably 10 to 180, most preferably 15 to 90 repeat units, where
the repeat units are selected
from the group consisting of (U), (V), (W), (X), (Y) and (Z).
As an alternative, it is preferable that the polyether-modified amino-
functional polybutadiene (G) or (K) has
on average 35 to 360, preferably 40 to 180, most preferably 45 to 90 repeat
units, where the repeat units
are selected from the group consisting of (U), (V), (W), (X), (Y) and (Z).
CA 03215157 2023- 10- 11
202000377 26
Most preferred are those polyether-modified amino-functional polybutadienes
(G) or (K) which are derived
from the polybutadienes (A) Polyvest 110 and Polyvest 130 from Evonik
Industries AG/Evonik Operations
GmbH and Lithene ultra AL and Lithene ActiV 50 from Synthomer PLC described
above.
The molar mass and polydispersity of the B radicals is freely variable.
However, it is preferable that the
average molar mass of the radical B is from 30 g/mol to 20 000 g/mol, more
preferably from 50 g/mol to 10
000 g/mol, even more preferably from 100 g/mol to 5000 g/mol, most preferably
from 150 g/mol to 1000
g/mol. The average molar mass of the B radicals may be calculated from the
starting weight of the
monomers used based on the number of OH and NH groups of the hydroxy- and
amino-functional
polybutadiene (E) used. Thus, for example, if 40 g of ethylene oxide are used
and the total amount of all
OH and NH groups of the hydroxy- and amino-functional polybutadiene (E) used
is together 0.05 mol, the
average molar mass of the B radical is 800 g/mol.
The polyether-modified amino-functional polybutadienes (G) or (K), according
to the composition and molar
mass, are liquid, pasty or solid.
The number-average molar mass (Ma) of the polyether-modified amino-functional
polybutadienes (G) or (K)
is preferably from 1000 g/mol to 50 000 g/mol, more preferably from 1500 g/mol
to 40 000 g/mol, even more
preferably from 2000 g/mol to 30 000 g/mol, most preferably from 3000 g/mol to
10 000 g/mol.
Their polydispersity (Mw/Mn) is variable within broad ranges. The
polydispersity of the at least one polyether-
modified polybutadiene (G) or (K) is preferably from 1.5 to 10, more
preferably from 2 to 8, most preferably
from 3 to 5.
The examples that follow describe the present invention by way of example,
without any intention that the
invention, the scope of application of which is apparent from the entirety of
the description and the claims,
be restricted to the embodiments specified in the examples.
Examples:
General methods:
Gel permeation chromatography (GPC):
GPC measurements for determination of the polydispersity (Mw/Mn), weight-
average molar mass (Mw) and
number-average molar mass (Ma) of the epoxy-functional polybutadiene (C) were
carried out under the
following measurement conditions: SDV 1000/10 000 A column combination (length
65 cm), temperature
30 C, THE as mobile phase, flow rate 1 ml/min, sample concentration 10 g/I, RI
detector, evaluation against
polypropylene glycol standard. GPC measurements for determination of the
polydispersity (Mw/Mn), weight-
average molar mass (Mw) and number-average molar mass (Ma) of the
polybutadienes (A) may be
conducted in the same manner.
CA 03215157 2023- 10- 11
202000377 27
GPC measurements for determination of the polydispersity (Mw/Mn), weight-
average molar mass (Mw) and
number-average molar mass (Ma) of the polyether-modified amino-functional
polybutadienes (G) in
accordance with the invention were carried out under the following measurement
conditions: J ordi DVB
500 A (length 30 cm), J ordi DVB Mixed Bed (length 30 cm) column combination,
temperature 30 C,
THF/triethylamine as mobile phase, flow rate 0.4 ml/min, sample concentration
3 g/I, RI detector, evaluation
against polystyrene standard. GPC measurements for determination of the
polydispersity (Mw/Ma), weight-
average molar mass (Mw) and number-average molar mass (Ma) of the end-capped
polyether-modified
amino-functional polybutadienes (K) may be conducted in the same manner.
Determination of the content of the 1,4-cis, 1,4-trans and 1,2 units in the
polybutadiene:
The content of 1,4-cis, 1,4-trans and 1,2 units can be determined with the aid
of 1H-NMR spectroscopy.
This method is familiar to the person skilled in the art.
Determination of the content of epoxy groups in the epoxy-functional
polybutadiene (C)(epoxy content,
degree of epoxidation)
The content of epoxy groups was determined with the aid of 13C-N MR
spectroscopy. A Bruker Avance 400
NMR spectrometer was used. The samples were for this purpose dissolved in
deuterochloroform. The
epoxy content is defined as the proportion of epoxidized butadiene units in
mol% based on the entirety of
all repeat units present in the sample. This corresponds to the number of
epoxy groups in the epoxy-
functional polybutadiene (C) divided by the number of double bonds in the
polybutadiene (A) used.
Determination of the acid value:
The acid value was determined by a titration method in accordance with DIN EN
ISO 2114.
Synthesis examples:
Step a), preparation of epoxidized polybutadienes
Example Al:
An epoxidized polybutadiene was prepared using a polybutadiene of the formula
(1) having the structure
x = 1%, y = 24% and z = 75% (Polyvest 110). According to the prior art, a
5- L reactor under a nitrogen atmosphere was initially charged with 1500 g of
Polyvest 110 and 146.3 g
of conc. formic acid in 1500 g of chloroform at room temperature.
Subsequently, 540 g of 30% H202 solution
(30% by weight H202 based on the total mass of the aqueous solution) was
slowly added dropwise and
then the solution was heated to 50 C for 7 hours. After the reaction had
ended, the mixture was cooled to
room temperature, the organic phase was removed and washed four times with
dist. H20. Excess
chloroform and residual water were distilled off. 1481 g of the product were
obtained, which was admixed
with 1000 ppm of Irganox 1135 and stored under nitrogen. Evaluation by means
of 13C-NMR gave a
CA 03215157 2023- 10- 11
202000377 28
degree of epoxidation of ca. 15.8% of the double bonds. GPC evaluation gave:
Mw = 4690 g/mol ; Mn =
1982 g/mol ; Mw/Mn = 2.4.
Step b), preparation of amino-functional polybutadienes
Example B1:
An amino-functional polybutadiene having a degree of amination of ca. 15.8%
was prepared using the
epoxidized polybutadiene prepared in Example Al. The degree of amination here
is the number of amino
groups of the amino-functional polybutadiene divided by the number of double
bonds in the polybutadiene
used in step a). For the preparation, 800 g of the epoxidized polybutadiene
with 136.3 g of ethanolamine
and 6.8 g of lithium bromide were initially charged in a 1 litre four-necked
flask under a nitrogen atmosphere
and the mixture heated at 180 C with stirring. The mixture was stirred at this
temperature for 15 hours. The
viscosity increased during the reaction. After the reaction was complete,
volatile components were removed
by distillation at 180 C and 20 mbar. The product was cooled to 60 C. 908 g of
a yellowish product were
obtained and stored under nitrogen. Evaluation by means of 13C-NMR showed
complete conversion of all
epoxy groups, which gives a degree of amination of ca. 15.8%.
Step c), alkoxylation of amino-functional polybutadienes
Example Cl:
A 1.5 litre autoclave was initially charged under nitrogen with 151 g of the
hydroxy- and amino-functional
polybutadiene prepared in Example B1 and heated to 115 C with stirring. The
reactor was evacuated down
to an internal pressure of 30 mbar in order to remove any volatile ingredients
present by distillation. 15.9 g
of ethylene oxide were fed in at 115 C over 5 minutes. The reactor internal
pressure rose to a maximum
value of 3.4 bar (absolute) and decreased continuously during the course of
the reaction. After 5.5 hours,
the pressure stabilized at 0.6 bar (absolute). Volatile components were
removed at 115 C and 20 mbar,
the reactor was depressurized to standard pressure with N2 and the reaction
mixture was cooled to 40 C.
26.9 g of 30% sodium methoxide solution (30% by weight sodium methoxide in
methanol based on the total
mass of the solution) were then added, the reactor contents inertized with
nitrogen and heated to 115 C
with stirring. The reactor internal pressure fell here to 20 mbar and methanol
was removed by distillation.
164.7 g of ethylene oxide were added at 115 C with stirring and cooling over
1.5 h at a maximum internal
pressure of 3.4 bar. During the post-reaction period of 3 h at 115 C, the
internal pressure fell continuously
until pressure stabilized at 0.5 bar (absolute). Volatile components such as
residual ethylene oxide were
distilled off under reduced pressure. The product was cooled to below 80 C,
neutralized with 14.9 g of 90%
lactic acid (90% by weight lactic acid in water based on the total mass of the
solution) to an acid number of
0.1 mg KOH/g, admixed with 1000 ppm Irganox 1135 and discharged. 317 g of a
viscous, orange-red
coloured, slightly cloudy polyether-modified amino-functional polybutadiene
were discharged and stored
under nitrogen. The total amount of ethylene oxide corresponded to an average
of 3.8 ethylene oxide units
per reactive NH/OH group. GPC evaluation gave: Mw = 19 484 g/mol ; Mn = 4474
g/mol ; Mw/Mn = 3.45.
Example C2:
A 1.5 litre autoclave was initially charged under nitrogen with 181 g of the
aminated polybutadiene prepared
CA 03215157 2023- 10- 11
202000377 29
in Example B1 and heated to 115 C with stirring. The reactor was evacuated
down to an internal pressure
of 30 mbar in order to remove any volatile ingredients present by
distillation. 25.2 g of propylene oxide were
fed in at 115 C over 5 minutes. The reactor internal pressure rose to a
maximum value of 2.4 bar (absolute)
and decreased continuously during the course of the reaction. After 4.5 hours,
the pressure stabilized at
0.7 bar (absolute). Volatile components were removed at 115 C and 20 mbar, the
reactor was
depressurized to standard pressure with N2 and the reaction mixture was cooled
to 40 C. 32.2 g of 30%
sodium methoxide solution (30% by weight sodium methoxide in methanol based on
the total mass of the
solution) were then added, the reactor contents inertized with nitrogen and
heated to 115 C with stirring.
The reactor internal pressure fell here to 20 mbar and methanol was removed by
distillation. 260 g of
propylene oxide were added at 115 C with stirring and cooling over 1.5 h at a
maximum internal pressure
of 2.9 bar. During the post-reaction period of 2 h at 115 C, the internal
pressure fell continuously until
pressure stabilized at 0.3 bar (absolute). Volatile components such as
residual propylene oxide were
distilled off under reduced pressure. The product was cooled to below 80 C,
neutralized with 17.9 g of 90%
lactic acid (90% by weight lactic acid in water based on the total mass of the
solution) to an acid number of
0.1 mg KOH/g, admixed with 1000 ppm Irganox 1135 and discharged. 421 g of a
viscous, orange-
coloured, slightly cloudy polyether-modified amino-functional polybutadiene
were discharged and stored
under nitrogen. The total amount of propylene oxide corresponded to an average
of 3.8 propylene oxide
units per reactive NH/OH group. GPC evaluation gave: Mw = 25 386 g/mol ; Mn =
5226 g/mol ; Mw/Mn = 4.86.
Example C3:
(Stoichiometry: 5 EO/5 PO per reactive NH/OH group)
A 1.5 litre autoclave was initially charged under nitrogen with 197 g of the
aminated polybutadiene prepared
in Example B1 and heated to 115 C with stirring. The reactor was evacuated
down to an internal pressure
of 30 mbar in order to remove any volatile ingredients present by
distillation. 27.4 g of propylene oxide were
fed in at 115 C over 5 minutes. The reactor internal pressure rose to a
maximum value of 2.3 bar (absolute)
and decreased continuously during the course of the reaction. After 4 hours,
the pressure stabilized at 0.7
bar (absolute). Volatile components were removed at 115 C and 20 mbar, the
reactor was depressurized
to standard pressure with N2 and the reaction mixture was cooled to 40 C. 17.6
g of 30% sodium methoxide
solution (30% by weight sodium methoxide in methanol based on the total mass
of the solution) were then
added, the reactor contents inertized with nitrogen and heated to 115 C with
stirring. The reactor internal
pressure fell here to 20 mbar and methanol was removed by distillation. A
mixture of 382 g of propylene
oxide and 310 g of ethylene oxide was added at 115 C with stirring and cooling
over 6 h at a maximum
internal pressure of 3.2 bar. During the post-reaction period of 2.5 h at 115
C, the internal pressure fell
continuously until pressure stabilized at 0.4 bar (absolute). Volatile
components such as residual propylene
oxide and ethylene oxide were distilled off under reduced pressure. The
product was cooled to below 80 C,
neutralized with 30% phosphoric acid (30% by weight phosphoric acid in water
based on the total mass of
the solution) to an acid number of 0.1 mg KOH/g, admixed with 500 ppm Irganox
1135 and discharged
via a filter. 881 g of a viscous, orange-coloured, clear polyether-modified
amino-functional polybutadiene
were discharged and stored under nitrogen. The total amount of ethylene oxide
and propylene oxide
corresponded to an average of 5 ethylene oxide units and 5 propylene oxide
units per reactive NH/OH
group. GPC evaluation gave: Mw = 32 145 g/mol ; Mn = 8349 g/mol ; Mw/Mn =
3.85.
CA 03215157 2023- 10- 11
